[0001] This invention relates to a new catalyst composition suitable for the polymerization
of a-olefins and to a polymerization process employing such a catalyst composition.
[0002] It is well known that olefins such as ethylene, propylene and 1-butene can be polymerized
in the presence ot metallic catalysts, particularly the reaction products of organometallic
compounds and transition metal compounds, to form substantially unbranced polymers
of relatively high molecular weight. Typically such polymerizations are carried out
at relatively low temperatures and pressures in an inert organic liquid diluent or
carrier. Following polymerization, it is common to remove catalyst residues from the
polymer by repeatedly treating the polymer with alcohol or other deactivating agent
such as aqueous base. Such catalyst deactivation and/or removal procedures are expensive
both in time and material consumed as well as the equipment required to carry out
such treatment.
[0003] Furthermore, most of the known catalyst systems are more efficient in preparing polyolefins
in slurry (i.e., wherein the polymer is not dissolved in the carrier) than in solution
(i.e., wherein the temperature is high enough to solubilize the polymer in the carrier).
The lower efficiencies of such catalysts in solution polymerization are generally
believed to be caused by the general tendency of the catalysts to become rapidly depleted
or deactivated by the higher temperatures normally employed in solution processes.
Also, processes involving the copolymerization of ethylene with higher a-olefins exhibit
catalyst efficiencies significantly lower than ethylene homopolymerization processes.
[0004] Recently, catalysts having'higher efficiencies have been disclosed as illustrated
by Scata U.S. Patent 4,115,319. While the increased efficiencies achieved by using
these recent catalysts are significant, even higher efficiencies are desirable particularly
in production of copolymers such as ethylene/hexene-1 or ethylene/octene-1 having
a low melt index at densities below 0.920 g/cc.
[0005] Also, these high efficiency catalyst generally produce polymers of relatively narrow
molecular weight distribution. It is therefore desirable to have, for some applications
such as injection molding, high efficiency catalysts which produce polymers and copolymers
having a broader molecular weight distribution.
[0006] The present invention, in one aspect, is a catalyst composition suitable for the
polymerization of a-olefins and prepared by reaction of: (A) a tetravalent titanium
compound or a complex of a trivalent titanium compound with an electron donor, (B)
an anhydrous divalent nickel compound, (C) an organomagnesium component, (D) a halide
source and (E) an alkylaluminum halide. The magnesium component is (1) an organomagnesium
compound or (2) a complex of an organomagnesium compound and an organometallic compound
in an amount sufficient to solubilize the organomagnesium compound in a hydrocarbon
solvent. The halide source is a non-metallic halide corresponding to the formula R'X
wherein R' is hydrogen or an active monovalent organic radical and X is halogen. Alternatively,
the halide source is a metallic halide correspond-. ing to the formula MR
y-aX
a wherein Group 2B, 3A or 4A of Mendeleev's Periodic Table of the Elements, R is a
monovalent organic radical usually hydrocarbyl or hydrocarbyloxy, X is halogen, y
is a number corresponding to valence of M and a is a number from 1 to y. The alkylaluminum
halide has the formula AlRy'Xy" wherein R is a monovalent organic radical and y' and
y" each have a value of from zero to three with the sum of y' and y" being three.
[0007] The proportions of the components of the catalyst reactants are such that the atomic
ratios of the elements are:
Mg:Ti is from 1:1 to 2000:1, preferably from 5:1 to 200:1; most preferably from 5:1 to 75:1;
Al:Ti is from 0.1:1 to 2000:1, preferably from 0.5:1 to 200:1; most preferably from
1:1 to 75:1;
Ni:Ti is from 0.01:1 to 500:1; preferably from 0.01:1 to 100:1; most preferably from
1:1 to 40:1;
excess X:A1 is from 0.002:1 to 10:1, preferably from 0.002:1 to 2:1, most preferably
from 0.01:1 to 1.4:1.
[0008] The "excess X" is excess halide above that which would be theoretically required
to convert the magnesium and nickel compounds to the dihalide if they were not added
in dihalide form.
[0009] In a second aspect, the invention is a process for polymerizing a-olefins under conditions
characteristic of Ziegler polymerization wherein the above catalyst is employed as
the sole catalyst. These catalysts are capable of producing more than a million pounds
of olefin polymer or copolymer per pound of transition metal. The resulting polymers
generally contain lower amounts of catalyst residues than polymers produced with conventional
catalyst even after treating to remove the catalyst. Further, these polymers have
a relatively broad molecular weight distribution.
[0010] The present invention is most advantageously practiced in a polymerization process
wherein an a-olefin is polymerized, generally in the presence of hydrogen as a molecular
weight control agent, in a polymerization zone containing an inert diluent and the
catalyst. The polymerization is most beneficially carried out under inert atmosphere
and relatively low temperature and pressure, although very high pressures are optionally
employed.
[0011] Olefins which are suitably homopolymerized or copolymerized in the practice of this
invention are aliphatic a-monoolefins or a-diolefins having from 2 to 18 carbon atoms.
Illustrative of such a-olefins are ethylene, propylene, butene-I, pen- tene-1, 3-methylbutene-1,
4-methylpentene-l, hexene-1, octene-1, dodecene-1, octadecene-1, 1,7-octadiene and
the like. It is understood that a-olefins may be copolymerized with other a-olefins
and/or with small amounts i.e., up to about 25 weignt percent based on the polymer
of other ethylenically unsalurated monomers such as styrene, a-methylstyrene and similar
ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts.
Most benefits are realized in the polymerization of aliphatic a-monoolefins, particularly
ethylene and mixtures of ethylene and up to 50, especially from 0.1 to 40 weight percent
of propylene, butene-1, hexene-1, octene-1, 4-methylpentene-l, 1,7-octadiene or similar
higher a-olefin or diolefin based on total monomer.
[0012] The anhydrous nickel compound (B) is required to obtain the broader molecular weight
distribution. Suitable nickel compounds include those nickel compounds represented
by the formula Ni(Q)
n wherein Q is an anion such as halide, particularly chloride or bromide, hydroxide,
carboxylate, carbonate, nitrate, sulfate or mixtures thereof and n is two (2) divided
by the valence of Q. Paticularly suitable nickel compounds are C1-C12 carboxylates,
and preferably C
6-C
10 carboxylates. Hydrocarbon soluble nickel carboxylates such as, for example, nickel
2-ethylhexanoate or naphthenate are particularly preferred since they form a smaller
particle size nickel chloride when prereacted with a suitable halogen source. However,
it is not necessary to prereact the nickel carboxylate with a halide source.
[0013] Advantageously, the tetravalent titanium compound has the empirical formula: TiXn(OR)4-n
wherein X is a halogen, particularly chlorine or bromine, R is an alkyl or an aryl
group having from 1 to 12 carbon atoms and n has a value of 0 to 4. Such titanium
compounds are preferably derived from the titanium halides wherein one or more of
the halogen atoms are replaced by an alkoxy or aryloxy group. Exemplary of such compounds
include tetrabutoxy titanium, tetra(isopropoxy) titanium, dibutoxy titanium dichloride,
monoethoxy titanium trichloride, tetraphenoxy titanium and the like.
[0014] Advantageously, the trivalent titanium complex has the empirical formula: TiX
3(L)
x wherein X is halide, and L is an electron donating compound such as water or an organic
electron donor, e.g., alcohol, ether, ketone, amine or olefin, and x is a number from
1 to 6. Usually, the organic electron donor has from 1 to 12 carbon atoms and donates
an unshared pair of electrons to the complex. In preferred complexes, X is chloride
or bromide, most preferably chloride and L is alcohol, especially an aliphatic alcohol
having 2 to 8 carbon atoms and most preferably 3 to 6 carbon atoms such as isopropyl
alcohol, n-propyl alcohol, n-butyl alcohol and isobutyl alcohol. While the exact structure
of the complex is not known, it is believed to contain 3 valence bonds to the halide
ions and 1 to 6, preferably 2 to 4 coordination bonds to the electron donating compound.
[0015] The titanium halide complex is most advantageously prepared by heating the trivalent
titanium halide dispersed in the electron donating compound under nitrogen or similar
inert atmosphere. Usually the formation of the complex is visually indicated by a
definite change in color. For example, when the dark purple α-TiCl
3 is heated in anhydrous iso- dark purple α-TiCl
3 is heated anhydrous propyl alcohol under nitrogen, complex formation is indicated
by the formation of a brilliant blue solution. The complex is normally solid, but
liquid complexes can be used.
[0016] In addition to a α-TiCl
3, the Δ, y and crystalline forms of titanium trichloride are advantageously employed
in the preparation of the complex. Also suitable are titanium tribromide, titanium
trifluoride and the like. Of the foregoing, the Δ- and a- forms of titanium trichloride
are preferred. Exemplary electron donating compounds include C
1-C
10 aliphatic alcohols, e.g., isopropyl alcohol, ethanol, n-propyl alcohol, butanol and
others; C
1-C
12 ethers, ketones, aldehydes, amines and olefins; and water.
[0017] The preferred organomagnesium component is a hydrocarbon soluble complex of the formula
MgR"
2·xMR"y wherein R" is a hydrocarbyl or hydrocarbyloxy, M is aluminum, zinc or mixtures
thereof and x is about 0.001 to 10, especially from about 0.15 to about 2.5, and y
denotes the number of hydrocarbyl groups which corresponds to the valence of M. As
used herein, hydrocarbyl and hydrocarbyloxy are monovalent hydrocarbon radicals. Preferably,
hydrocarbyl is alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon radicals
having 1 to 20 carbon atoms, with alkyl having 1 to 10 carbon atoms being especially
preferred. Likewise, preferably, hydrocarbyloxy is alkoxy, cycloalkyloxy, aryloxy,
aralkyloxy, alkenyloxy and similar oxyhydrocarbon radicals having 1 to 20 carbon atoms,
with alkyloxy having 1 to 10 car-. bon atoms preferred. Hydrocarbyl is preferred over
hydrocarbyloxy.
[0018] This complex is prepared by reacting particulate magnesium such as magnesium turnings,
or magnesium particles with about a stoichiometric amount of hydrocarbyl or hydrocarbyloxy
halide, illustrated as R'X. The resulting hydrocarbon insoluble MgR"
2 is solubilized by adding the organometallic compound such as AlR"
3 or mixtures thereof with ZnR"
2. The amount of organometallic compounds which is added to the MgR"
2 to form the organomagnesium complex should be enough to solubilize a significant
amount of MgR"
2, e.g., at least 5 weight percent, preferably at least 50 weight percent, and especially
preferred all the MgR"
2' When employing a mixture of AlR"
3 and ZnR"
2 to solubilize MgR"
2, the atomic ratio of Zn to Al is from about 3000:1 to about 0.1:1, preferably from
about 350:1 to about 1:1.
[0019] In order to obtain maximum catalyst efficiency at polymerization temperatures above
180°F, it is desirable to minimize the amount of aluminum in the complex and the total
catalyst. Accordingly, for catalysts having Al:Ti atomic ratios less than 120:1, it
is desirable to have a Mg:Al atomic ratio more than 0.3:1, preferably from about 0.5:1
to 10:1.
[0020] Other organometallic compounds than AlR"
3' ZnR" or mixtures thereof can be used to solubilize the organomagnesium compound in
hydrocarbon, usually in an amount sufficient to produce an atomic ratio of 0.01:1
to 10:1 of metal nf The organometallic compounds to magnesium. Examples of other organometallic
compounds include boron trialkyls such as boron triethyl, alkyl silanes such as dimethyl
silane and tetraethyl silane, alkyl-tin and alkyl phosphorous compounds.
[0021] Alternatively, organomagnesium compounds can be used without an aluminum or zinc
complex particularly if rendered soluble in hydrocarbon by addition of ether, amine,
etc. More recently, hydrocarbon soluble organomagnesium compounds have been prepared
as taught in Kamienski et al. U.S. 3,646,231. These organomagnesium compounds are
particularly desirable.
[0022] Preferably the organomagnesium compound is a hydrocarbon soluble dihydrocarbylmagnesium
such as the magnesium dialkyls and the magnesium diaryls. Exemplary magnesium dialkyls
include n-butyl-sec-butyl magnesium, diisopropyl magnesium, di
-n-hexyl magnesium, isopropyl-n-butyl magensium, ethyl-n-hexyl magnesium, ethyl-n-butyl
magnesium, di-n-octyl magnesium and others wherein alkyl has from 1 to 20 carbon atoms.
Exemplary magnesium diaryls include diphenylmagnesium, dibenzylmag- nesium, and especially
preferred ditolylmagnesium. Also suitable are alkyl and aryl magnesium alkoxides and
aryloxides and aryl and alkyl magnesium halides with the halogen-free organomagnesium
compounds being more desirable.
[0023] The preferred halide sources are the active non-metallic halides of the formula R'X
including hydrogen halides and active organic halides such as t-alkyl halides, allyl
halides, benzyl halides and other active hydrocarbyl halides. By an active organic
halide is meant a hydrocarbyl halide that contains a labile halogen at least as active,
i.e., as easily lost to another compound, as the halogen of sec-butyl chloride and
preferably as active as t-butyl chloride. Active organic dihalides, trihalides and
poly- halides are also suitably employed. Examples of preferred active non-metallic
halides are hydrogen chloride, hydrogen bromide, t-butyl chloride, t-amyl bromide,
allyl chloride, benzyl chloride, crotyl chloride, methylvinyl carbinyl chloride, a-phenylethyl
bromide and diphenyl methyl chloride.
[0024] Most preferred are hydrogen chloride, t-butyl chloride, allyl chloride and benzyl
chloride.
[0025] Suitable metallic halides as set forth by formula hereinbefore are organometallic
halides and metal halides wherein the metal is in Group 2B, 3A or 4A, of Mendeleev's
Periodic Table of Elements. Preferred metallic halides are aluminum halides of the
formula AlR
3-aX
a wherein each R is independently hydrocarbyl such as alkyl, X is a halogen, and a is
a number from 1 to 3. Most preferred are alkylaluminum halides such as ethylaluminum
sesquichloride, diethyl-aluminum chloride, ethylaluminum dichloride, and diethyl-aluminum
bromide, with ethylaluminum dichloride being especially preferred. Alternatively,
a metal halide such as aluminum trichloride or a combination of aluminum trichloride
with an alkyl aluminum halide or trialkyl aluminum compound may be employed.
[0026] The organic moieties of the aforementioned organomagnesium, e.g., R", and the organic
moieties of the halide source, e.g., R and R', are suitably any other organic radical
provided that they do not contain functional groups that poison conventional Ziegler
catalysts. Preferably such organic moieties do not contain active hydrogen, i.e.,
those sufficiently active to react with the Zere- witinoff reagent.
[0027] In cases wherein neither the organomagnesium component nor the halide source contains
aluminum, it is desirable to include in the total catalyst an aluminum compound such
as an alkyl aluminum compound, e.g., a trialkyl aluminum, an alkyl aluminum halide
or an aluminum halide.
[0028] In order to maximize catalyst efficiency, the catalyst is prepared by mixing the
components of the catalyst in an inert liquid diluent in the following especially
preferred order: nickel compound, organomagnesium compound, halide source and titanium
compound or complex. Somewhat less preferred is the order of addition wherein the
organomagnesium component is first added to an inert liquid diluent followed by the
addition of the halide source, the nickel compound and then the titanium compound
or complex. The foregoing catalyst components are combined in proportions sufficient
to provide atomic ratios as previously mentioned.
[0029] In the most preferred manner, the nickel halide is preformed from the reaction of
a hydrocarbon soluble nickel carboxylate such as nickel di-2-ethylhexanoate or nickel
dinaphthenate with the halogen source in a hydrocarbon diluent which precipitates
anhydrous nickel halide in a very fine particulate form.
[0030] If polymerization temperatures below 180°C are employed, the atomic ratios of Al:Ti
may be from 0.1:1 to 2000:1, preferably from 1:1 to 200:1. However, when polymerization
temperatures above 180°C are employed, the aluminum compound is used in proportions
such that the Mg:Al ratio is more than 0.3:1, preferably from 0.5:1 to 10:1, and Al:Ti
ratio is less than 120:1, preferably less than 75:1. The use of very low amounts of
aluminum necessitates the use of high purity solvents or diluents in the polymerization
zone and other components should be essentially free of impurities which react with
aluminum alkyls. Otherwise additional quantities of an organomet- tallic compound
must be used to react with such impurities. Moreover, in the catalyst the aluminum
compound should be in the form of trialkyl aluminum or alkyl aluminum halide substantially
free of alkyl aluminum dihalide.
[0031] The catalytic components are preferably combined in the presence of an inert liquid
diluent such that the resultant catalyst slurry is from 0.005 to 1.0 molar (moles/liter)
with respect to magnesium. Suitable inert organic diluents include liquefied ethane
propane, isobutane, u-butane , n-hexane, the various isomeric hexanes, isooctane,
paraffinic mixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane,
dimethylcyclohexane, dodecane and industrial solvents composed of saturated or aromatic
hydrocarbons such as kerosene, naphthas, etc., especially when freed of any olefin
compounds and other impurities, and having boiling points in the range from -50° to
200°C. Also included as suitable inert diluents are benzene, toluene, ethylbenzene,
cumene and decaline.
[0032] Mixing of the components to provide the desired catalyst is advantageously carried
out under an inert atmosphere such as nitrgoen or argon at temperatures in the range
from -100 to 200°C, preferably from 0° to 100°C. The mixing time is not critical as
an active catalyst most often is formed in 1 minute or less. In the preparation of
the catalyst, it in not necessary to separate hydrocarbon soluble and insoluble components.
[0033] Polymerization of a-olefins is effected by contacting a catalytic amount of the catalyst
composition and the a-olefin monomer at temperatures in the range from 0 to 300°C,
and preferably at solution polymerization temperatures, e.g., from 130° to 250°C,
for a residence time of a few seconds to 48 hours or more, preferably 15 seconds to
2 hours. Also it is generally desirable to carry out the polymerization in the absence
of moisture and oxygen using an inert liquid carrier which may be an organic diluent,
solvnet, or excess monomer. Diluents employed in the catalyst preparation are particularly
suitable.
[0034] To obtain maximum catalyst yields in terms of polymer weight per weight of titanium,
sufficient catalyst should be used to provide from 0.0001 to 0.1 millimoles titanium
per liter of diluent in the polymerization zone. However, the optimum catalyst concentration
will depend upon polymerization conditions such as temperature, pressure, solvent
and presence of catalyst poisons.
[0035] To realize the full benefit of the high efficiency catalyst, care must be taken to
avoid oversaturation of the solvent with polymer.
[0036] To optimize catalyst yields in the polymerization of ethylene, it is preferable to
maintain an ethylene concentration in the solvent in the range from 1 to 10 weight
percent and most advantageously 1.2 to 2 weight percent. Also care must be taken to
avoid oversaturation of the solvent with the resulting polymer. For best results,
the amount of polymer in the carrier should not exceed about 50 weight percent based
on the total weight of the reaction mixture.
[0037] Hydrogen can be employed in concentrations ranging from 0.001 to 1 mole per mole
of monomer to reduce the molecular weight of the resultant polymer by addition with
the monomer stream or other conventional means.
[0038] The preferred polymerization pressures are relatively low, e.g., from 50 to 1000
psig (3.5--70 kg/cm
2 gauge) especially from 100 to 600 psig (7.0-42 kg/cm
2 gauge). However, polymerization can occur at pressures from atmospheric to the pressure
limit of the reactor. Stirring during polymerization is desirable to maintain better
temperature control and more uniform concentrations throughout the polymerization
zone.
[0039] The a-olefin monomer or mixture of monomers is contacted with the catalyst in the
usual manner, preferably by bringing the catalyst and monomer together with intimate
agitation provided by stirring or other means. Agitation can be continued during polymerization,
but in some instances polymerization in an unstirred zone is desirable. Adequate means
should be provided for dissipating the exothermic heat of polymerization. With more
active catalyst, means for refluxing monomer and solvent is often advantageous.
[0040] The polymerization can be effected in batch or continuous manner, such as, for example,
by passing the reaction mixture through an elongated reaction tube which is contacted
externally with suitable cooling medium to maintain the desired reaction temperature,
or by passing the reaction mixture through an equilibrium overflow reactor or a series
of the same.
[0041] The polymer is recovered from the polymerization mixture by removing any unreacted
monomer and solvent. No further purification is required. In some instances, however,
it may be desirable to add a small amount of a conventional catalyst deactivating
reagent. The resultant polymer contains insignificant amounts of catalyst residue
and possesses a relatively broad molecular weight distribution.
[0042] The following examples are given to further illustrate the invention. All parts and
percentages are by weight unless otherwise indicated. The melt index values 1
2 and I
10 were determined by the method of ASTM D 1238-70 and the density values were determined
by ASTM D 1248-74.
[0043] In Examples 1-7, the catalysts were prepared in n-heptane, 2,2,4-trimethylpentane
or Isopar® E (a mixture of saturated isoparaffins having 8 to 9 carbon atoms) under
nitrogen atmosphere containing less than 5 ppm oxygen and 5 ppm water. Polymerizations
were carried out in five liter stainless steel stirred batch reactor using two liters
of dry, oxygen-free Isopar® E as carrier diluents. After polymerization, the reactor
contents were dumped into a beaker, cooled, and the polymer recovered, dried in a
vacuum oven and analyzed. The melt index values I
2 and I
10 were determined by the method of ASTM D-1238-70 and the density values by the method
of ASTM D-1248. Catalyst efficiencies are reported as grams of polyethylene per gram
of titanium, gPE/gTi.
EXAMPLE 1 Polyethylene
A. Preparation of Anhydrous NiCl2
[0044] An anhydrous nickel chloride (NiCl
2) slurry in isopar® E was prepared as follows. NiCl
2·6H
2O was heated in a vacuum oven at about 100°C for 8-10 hours. The resultant partially
dried product was then extracted with n-propyl alcohol into Isopar® E to produce a
fine slurry of anhydrous NiCl
2 in Isopar® E. The n-propyl alcohol was then removed by distillation.
B. Preparation of the Catalyst Composition
[0045] The catalyst composition was prepared by adding with stirring to a 4-ounce (118 cc)
serum bottle under a nitrogen atmosphere the following components in the indicated
order:
[0046] 48.45 ml of Isopar® E 0.18 ml of 0.084 M anhydrous NiCl
2 in Isopar
® E 0.74 ml of 0.385 M Mg(n-Bu, sec-Bu) in Isopar
® E 0.44 ml of 0.85 M EtAlCl
2 in Isopar® E 0.19 ml of 0.04 M Ti(OiPr)
4 in Isopar
® E
[0047] The reaction was complete within 5 minutes at ambient temperature.
[0048] The atomic ratios of the catalyst components were as follows:
Mg/Ti = 38:1 Al/Ti = 50:1 Ni/Ti = 2:1 excess Cl/Al = 24:50 = 0.48:1
C. Polymerization
[0049] Into the stirred 5-liter stainless steel reactor was added two liters of Isopar®
E, 19 psig (1.3 kg/cm
2 gauge) of hydrogen, 120 psig (8.4 kg/cm
2 gauge) of ethylene. The reactor was heated to 150°C and then 10 ml (0.0015 millimoles
Ti) of the above catalyst composition was added. The temperature was controlled at
150°C and the total pressure was maintained constant at 160 psiq (11.2 kg/cm
2 gauge) for 20 minutes yielding 100 grams of polyethylene, a catalyst efficiency of
1.14 x 10
6 grams of polymer per gram of Ti. The polymer had a melt index (I
2) of 4.35, a melt index (I
10) of 38.72, an
I10/
I2 of 8.9 and a density of 0.9647 g/cc.
EXAMPLE 2 Ethylene/1-Hexene Copolymer
[0050] A. Employing the procedures of Example 1, a catalyst was prepared using the following
components listed in order of addition:
42.12 ml of Isopar® E .45 ml of 0.084 M anhydrous NiCl2 5.8 ml of 0.045 M MgCl2 (prepared from HC1 and n-Bu-s-Bu-Mg) .09 ml of 0.85 M ethylaluminum dichloride .33
ml of 0.9 M aluminumtriethyl 1.21 ml of 0.0062 M TiCl3(iPrCH)x
[0051] The atomic ratios of this catalyst were as follows:
Mg/Ti = 35:1
Al/Ti = 50:1
Ni/Ti = 5:1 excess C1/A1 = 0.4:1
[0052] B. Polymerization was conducted as described in Example 1 at 150°C using twenty (20)
milliliters of hexene-1, 20 psig (1.4 kg/cm
2 gauge) H
2 and 120 psig (8.4 kg/cm
2 gauge) ethylene. The final reactor pressure was 165 psig (11.6 kg/cm
2 gauge). Twenty milliliters (0.003 millimoles of Ti) of the catalyst yielded 156 grams
of polymer for an effeciency of 1.1 x 10
6 g polymer/g Ti. The polymer had a broad molecular weight distribution with a high
molecular weight tail as indicated by gel permeation chromatography and the following
properties:
0.69 melt index (12) 8.14 (I10) 11.8 I10/ I2 0.9427 g/cc density
EXAMPLE 3
EXAMPLE 4
A. Preparation of Anhydrous NiCl2
[0054] To a mixture of .60 gram (0.5 millimoles) of a nickel di-2-ethylhexanoate solution
in mineral spirits containing 6% Ni by weight (commercially available from the Ventron
Corp., Danvers, Mass.) and 97.8 ml of 2,2,4-trimethyl pentane (TMP) was added 1.65
ml of 0.94 M (1.5 moles) ethyl aluminum dichloride (EADC). Immediately upon addition
of the EADC, a fine particle size, gold colored slurry of NiCl
2 was formed.
B. Preparation of the Catalyst Composition
[0055] The catalyst was prepared by reacting at ambient temperature under a nitrogen atmosphere
the following components in the indicated order:
94.47 ml TMP 3.0 ml of the 0.005 M Nicl2 in TMP 0.97 ml of 0.62 M butyl ethyl magensium (BEM) 0.64 ml of 0.94 M EADC 0.32
ml of 0.91 M triethylaluminum (ATB) in TMP 0.60 ml of 0.025 M tetra-isopropyl titanate
(Ti(OiPr)4) in TMP.
[0056] The reaction was complete within 5 minutes or less.
[0057] The atomic ratios of the catalyst components were as follows:
Mg/Ti = 40:1 Al/Ti = 60:1 Ni/Ti = 1:1 excess Cl:Al = 0.1:1
C. Polymerization
[0058] As described in Example 1C, the 5-liter reactor charged with 2 liters of Isopar®
E was heated to 150°C and then was added 19 psig (1.3 kg/cm
2 gauge) of hydrogen and 160 psig (11.2 kg/cm
2 gauge) of ethylene added for a total reactor pressure of 200 psig (14.0 kg/cm
2 gauge). Twenty ml (0.003 moles of Ti) of the catalyst (4B) was injected into the
reactor, and the pressure maintained at 200 psig (14.0 kg/cm
2 gauge) with ethylene for 30 minutes. A yield of 177 gm of polyethylene (1.23 x 10
6 gm PE/gm Ti) was obtained with a melt index of 0.78, an I
10 of 8.70, I
10/I
2 of 11.15, and a density of 0.9610.
EXAMPLE 5
[0059] Following the general procedure of Example 4, several other catalyst were prepared
using NiCl
2 formed in situ and evaluated using a total catalyst concentration of 0.001 millimolar
based on Ti and a polymerization temperature of 150°C. Unless otherwise indicated
the ethylene pressure was 120 psig (8.4 kg/cm
2 gauge) and the total pressure was 160 psig (11.2 kg/cm
2 gauge). Typical data are given in Tables III and IV.
EXAMPLE 6
[0060] Data from another series of catalysts prepared and evaluated as described in Example
4 are given in Tables V and VI. Unless otherwise indicated, the total catalyst concentration
was 0.001 millimolar based on Ti, the polymerization temperature was 150°C, and the
ethylene pressure was 160 psig (11.2 kg/cm
2 gauge) and the total pressure 200 psig (14.0 kg/cm
2 gauge).
EXAMPLE 7 Ethylene/1-Octene Copolymers
[0061] Data from another series of catalysts prepared as described in Example 4 and evaluated
for the polymerization of ethylene/1-octene are given in Tables VII and VIII. Unless
otherwise indicated, the total catalyst concentration was 0.001 millimolar based on
Ti and the polymerization temperature was 150°C. The reactor was charged with 150
psig (10.5 kg/cm
2 gauge) of ethylene, and 200 ml of 1-octene as comonomers. No hydrogen was added.
The total reactor pressure was 200 psig (
14.0 kg/cm
2 gauge).
1. A catalyst composition suitable for the polymerization of a-olefins and prepared
by reaction of:
(A) a tetravalent titanium compound or a complex of a trivalent titanium compound
with an electron donor,
(B) an anhydrous divalent nickel compound,
(C) an organomagnesium component selected from (1) an organomagnesium compound or
(2) a complex of an organomagensium compound and an organometallic compound in an
amount safficient to solubilize the organomagnesium compound in a hydrocarbon solvent,
(D) a halide source selected from (1) an active non-metallic halide, said non-metallic
halide corresponding to the formula R'X wherein R' is hydrogen or an organic group
at least as active as sec-butyl and X is halogen or (2) a metallic halide corresponding
to the formula MRy-aXa wherein M is a metal of Group 2B, 3A or 4A of Mendeleev's Periodic Table of Elements,
R is a monovalent organic radical, X is halogen, y is a number corresponding to the
valence of M and a is a number of 1 to y, and
(E) an aluminum compound represented by the formula AlRy'Xy" wherein R and X are as
defined above and y' and y" each have a value of from zero to three with the sum of
y' and y" being three if the organomagnesium component (B) and/or the halide source
(D) provides sufficient quantities of aluminum; provided that the proportions of components
(A)-(E) are such that the atomic ratio of Mg:Ti is from 1:1 to 2000:1, the atomic
ratio of Al:Ti is from 0.01:1 to 2000:1, the atomic ratio of Ni:Ti is from 0.01 to
500:1, the atomic ratio of excess halide:Al X is from 0.0005:1 to 10:1.
2. The catalyst composition of Claim 1 where the nickel compound (B) is nickel halide
and the atomic ratios of Mg:Ti, Al:Ti, Ni:Ti, and excess halide:Al are respectively
from 5:1 to 200:1, from 0.5:1 to 200:1, from 0.1:1 to 100:1, and from 0.002:1 to 2:1.
3. The catalyst composition of Claim 1 where the nickel compound (B) is nickel chloride,
the halide source (D) is an alkyl aluminum chloride, and the atomic ratios of Mg:Ti,
Al:Ti, Ni:Ti, and excess chloride:Al are respectively from 5:1 to 75:1, from 1:1 to
75:1, from 1:1 to 40:1, and from 0.01 to 1:4.
4. The catalyst composition of Claim 3 where the nickel compound (B) is a hydrocarbon
soluble nickel C1-C12 carboxylate.
5. The catalyst composition of Claim 3 where the nickel compound (B) is 2-ethylhexanoate
or nickel naphthenate and the halide source (D) is ethyl aluminum dichloride.
6. The catalyst composition of Claim 1 where the nickel chloride is formed in situ
by reaction of a hydrocarbon soluble nickel C6-C10 carboxylate with an active halide source (D).
7. The catalyst composition of Claim 1 where (a) is tetra(isopropoxy)titanium, (B)
is anhydrous nickel chloride, (C) is a dialkyl magnesium complex with ethyl aluminum
dichloride with an atomic ratio of Mg:Al of from 0.3:1 to 1000:1, (D) is hydrogen
chloride, diethyl aluminum chloride or ethyl aluminum dichloride; and the atomic ratios
of Mg:Ti, Al:Ti, Ni:Ti, and excess Cl:Al are respectively from 5:1 to 75:1, from 1:1
to 75:1, from 1:1 to 40:1, and from 0.01 to 1.4.
8. A process for the polymerization of an α-olefin under conditions characteristic
of Zeigler polymerization which comprises employing as the polymerization catalyst
the composition of any one of Claims 1 to 7.
9. The process of Claim 8 where the nickel compound is anhydrous nickel chloride.
10. The process of Claims 8 or 9 where the a-olefin is ethylene or a mixture of ethylene
and at least one other copolymerizable, ethylenically unsaturated monomer.